CN1199299C - Cadmium cathode and Ni-Cd accumulator comprising same - Google Patents

Cadmium cathode and Ni-Cd accumulator comprising same Download PDF

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Publication number
CN1199299C
CN1199299C CNB021505802A CN02150580A CN1199299C CN 1199299 C CN1199299 C CN 1199299C CN B021505802 A CNB021505802 A CN B021505802A CN 02150580 A CN02150580 A CN 02150580A CN 1199299 C CN1199299 C CN 1199299C
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Prior art keywords
cadmium
battery
pole plate
cathode
nickel
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Expired - Fee Related
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CNB021505802A
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CN1420575A (en
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丸田雅义
森田美加
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/10—Electroplating: Baths therefor from solutions of chromium characterised by the organic bath constituents used
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/246—Cadmium electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • H01M4/742—Meshes or woven material; Expanded metal perforated material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A cadmium negative electrode for a nickel cadmium storage battery, the electrode comprising an electrode plate and a resin layer coating at least one surface of the electrode plate, the electrode plate comprising a cadmium compound as an active material, the resin layer comprising polyvinyl pyrrolidone and a product of an addition reaction of a styrylpyridinium salt to polyvinyl alcohol.

Description

Cadmium cathode and the cadmium-nickel storage cell that comprises it
Technical field
The present invention relates to cadmium cathode and the cadmium-nickel storage cell that comprises it.
Background technology
At present, in the secondary cell based on lithium secondary battery, nickel-hydrogen accumulator, but, cadmium-nickel storage cell is because the efficient discharge characteristic is good and have the long good characteristic of charge and discharge circulation life, and is being extensive use of to fields such as cosmic space exploitations from civilian small-sized machine.But, can dissolve repeatedly and separate out, so have the phenomenon of separating out, put aside of cadmium to occur at the pore place of dividing plate owing to discharge and recharge its negative electrode active material for cadmium-nickel storage cell.These phenomenons are called as migration, are the reasons that causes anodal and negative pole short circuit.
Particularly become use main flow, that can obtain high energy density cells at low cost in recent years and stick with paste the battery of formula negative pole, it is compared with sintered type negative pole in the past, has significantly migration.This is that active material is kept in the matrix (マ ト リ Star Network ス) of sintering metal owing to the sintered type negative pole, and the formula of paste negative pole owing to use the organic material of the active material that can bond, does not therefore possess aforesaid matrix.These organic materials are during along with the cycle charge-discharge of battery and during oxidation and decompose, and original active material are fixed on effect in the pole plate so can not play.This is the reason that produces migration.If therefore improve the packed density of active material in the negative pole in order to realize high capacity, the change meeting of active material volume is whole when then discharging and recharging becomes big, thereby quickens migration.
For the short circuit that prevents to be caused by migration, the spy opens the hybrid resin layer that proposes to form in negative terminal surface polyvinylpyrrolidone and polyvinyl alcohol in the flat 5-283067 communique.Can prevent to discharge and recharge the diffusion of cadmium in dividing plate in the electrolyte of stripping in the reaction so to a certain extent.
But, the short circuit in order fully to prevent to be caused by migration in the above-mentioned example in the past must form thick resin bed in negative terminal surface.Therefore, negative terminal surface can form dielectric tunicle, thus the problem that the absorption of oxygen is hindered when existing the battery-efficient flash-over characteristic low, overcharged.Main purpose of the present invention is to provide cadmium cathode, and it can be supplied with negative pole and form thick resin bed but can not cause that the battery-efficient flash-over characteristic reduces and the cadmium-nickel storage cell of charge and discharge circulation life excellence uses.
Summary of the invention
The present invention relates to the cadmium-nickel storage cell cadmium cathode, described cadmium cathode is made of pole plate and the resin bed that is coated on described polar board surface, described pole plate is active material with the cadmium compound, and described resin bed is made of product and the polyvinylpyrrolidone with addition reaction polyvinyl alcohol stibazole salt.
Use this cadmium cathode can obtain that the efficient discharge characteristic does not reduce and the cadmium-nickel storage cell of cycle life excellence.
Aforementioned cadmium cathode preferably has the conductive layer that is made of metallic nickel between aforementioned pole plate and aforementioned resin layer.
The present invention relates to prepare the method for cadmium-nickel storage cell with cadmium cathode, it comprise obtain with cadmium compound contain as operation (a), the preparation of the pole plate of active material the product of stibazole salt and addition reaction polyvinyl alcohol and polyvinylpyrrolidone the aqueous solution operation (b) and aqueous solution is coated in aforementioned polar board surface or aforementioned pole plate is immersed in operation (c) in the aqueous solution.
Aforementioned preparation method preferably has at aforementioned polar board surface by electroplate forming the operation of the conductive layer that is made of metallic nickel in that operation (c) is preceding.
In addition, the invention still further relates to by nickeliferous positive pole, above-mentioned cadmium cathode, be present in the cadmium-nickel storage cell that dividing plate between aforementioned positive pole and the negative pole and alkaline electrolyte constitute.
Brief Description Of Drawings
Fig. 1 is the cross-section model of negative pole a in the embodiment of the invention 1.
Fig. 2 is the cross-section model of negative pole b in the embodiment of the invention 2.
Fig. 3 is the charge and discharge cycles number of battery A～E and the graph of a relation of discharge capacity.
Fig. 4 is the graph of a relation of the amount of cadmium in the charge and discharge cycles number of battery A～E and the dividing plate.
Fig. 5 is the discharge curve of battery A～E.
Detailed Description Of The Invention
Cadmium cathode of the present invention is characterized in that, its surface is by by styryl pyridinium With the product of the addition reaction of polyvinyl alcohol and the resin bed institute that polyvinylpyrrolidone consists of Coating. Use by the product of styryl pyridinium and addition reaction polyvinyl alcohol and poly-During resin bed coating negative terminal surface that vinylpyrrolidone consists of, can obtain thin than in the past Many and bruly wood fat layer. The thickness of resin bed for example is 0.05～3 μ m, is preferably 0.1～2 μ m. Because resin bed is thin, do not reduce so can not cause the battery-efficient flash-over characteristic, this Outer resin bed can suppress to follow the cadmium of charge and discharge cycles to the stripping of electrolyte, thereby can get To the cadmium-nickel storage cell that has extended cycle life.
Even all surfaces of the preferred coating negative pole of resin bed is but the part table of coating negative pole only Face also can play according to its area and to suppress cadmium to the effect of electrolyte stripping etc.
Cadmium cathode of the present invention preferably further has by the metallic nickel structure between pole plate and resin bed The conductive layer that becomes. The conductive layer that setting is made of metallic nickel can be kept the high conduction of paste-type negative pole The property.
The thickness of the conductive layer that is made of metallic nickel for example is 2～15 μ m, is preferably 4～7 μ M.
The molal quantity of the hydroxyl that has with respect to polyvinyl alcohol is with the benzene second of polyvinyl alcohol addition The amount of thiazolinyl pyridiniujm is preferably 0.5～2 % by mole, but is not limited to this.
In addition, with the amount of the styryl pyridinium of polyvinyl alcohol addition be, usually with respect to Per 100 weight account polyethylene alcohol, it is 5～15 weight portions.
The weight ratio of contained polyvinyl alcohol and polyvinylpyrrolidone is preferably in the resin bed, and per 100 weight account polyethylene pyrrolidones, polyvinyl alcohol are 10～30 weight portions.
The number average degree of polymerization of polyvinyl alcohol preferred 100～10000.In addition, the number average degree of polymerization of polyvinylpyrrolidone preferred 100～10000.Polyvinylpyrrolidone for example can use the polymer of N-ethene-2 pyrrolidones.
Stibazole salt general expression
Expression.Here, R 1For having the group of carbonyl (C=O), be preferably formoxyl.R 1With the hydroxyl reaction of polyvinyl alcohol, thereby make stibazole salt and polyvinyl alcohol generation addition.
R 2, R 3Respectively independent, for carbon number is 1～3 alkyl, R 2, R 3At least one side with constitute salt in abutting connection with six membered ring.Stibazole salt is sometimes owing to dimerization takes place in light reaction.
Because the dimerization of stibazole salt, negative terminal surface can form membranoid substance, thereby can play the effect that prevents that negative material from coming off.
Negative pole of the present invention for example can be obtained by following main points.
At first preparation contains and is the pole plate of active material with the cadmium compound.Can prepare pole plate samely, for example can stick with paste (Negative Very closes drug ペ one ス ト) and be coated on punch metal, the bar sheetmetal cores such as (ラ ス メ Le) and obtain by the cathode agent that will contain cadmium compound.Cadmium compound preferably uses the cadmium oxide of average grain diameter 0.3～1.0 μ m.Cadmium compound preferably mixes use with cadmium metal.
Then, form resin bed at polar board surface.Can enumerate as method for optimizing, preparation contain the product of stibazole salt and addition reaction polyvinyl alcohol and polyvinylpyrrolidone the aqueous solution and with aqueous solution be coated on polar board surface method, pole plate is immersed in method in the aqueous solution.In the aqueous solution, the composition of required resin bed is lumped together, make each resin dissolves.The total concentration of resinous principle is preferably 0.1～3.0 weight % in the aqueous solution.
Be provided with between pole plate and the resin bed under the situation of the conductive layer that constitutes by metallic nickel, preferably before polar board surface forms resin bed, carrying out implementing the operation of electrolytic ni plating at polar board surface.The thickness of the conductive layer that is made of metallic nickel is preferably 0.1～1.0 μ m.
Below embodiments of the invention are described.
Embodiment 1
Fig. 1 is the cross-section model of cadmium cathode made in the present embodiment.
With 80 weight portion average grain diameters be 0.5 μ m cadmium oxide, 20 weight portion average grain diameters, 2 μ m cadmium metal with as reinforcing agent, that 30 weight portions contain the ethylene glycol solution (PVA concentration 1.5 weight %) of polyvinyl alcohol (PVA) of the fiber that 1 weight % is made of the copolymer of acrylonitrile and ethlyene dichloride is mixing, obtains the cathode agent paste.
The thickness that this paste is coated on through nickel plating is the two sides of the punch metal 13 of 100 μ m, and the dry anode mixture layer 12 that forms obtains pole plate X1.This pole plate X1 is immersed in the potassium hydroxide aqueous solution of 30 ℃ of proportions 1.23, temperature, makes cadmium oxide be converted into cadmium hydroxide, obtain pole plate X2.
Then modulation contains with N-methyl-4-(p-formyl styrene) pyridine dimethyl suflfate: N-methy1-4 (p-formylstyry1) pyridiniummethosulfate (below be designated as stibazole sulfate) with the concentration of 10 weight % the (number average degree of polymerization: the aqueous solution 1700) of the polyvinyl alcohol after the addition has taken place.With the amount of the stibazole sulfate of polyvinyl alcohol generation addition be that with respect to 10 weight account polyethylene alcohol, it is 1 weight portion.
With obtained aqueous solution 1 weight portion, (number average degree of polymerization: the aqueous solution 4 weight portions 1700) join in the water of 95 weight portions and obtain mixed aqueous solution to contain the polyvinylpyrrolidone of 30 weight %.
The above-mentioned pole plate X2 that contains cadmium hydroxide is immersed in the aforementioned mixed aqueous solution, and drying has formed the resin bed 11 of about 0.1～2 μ m of thickness on the surface of pole plate X2.So just finished paste formula cadmium cathode a.
Use the dividing plate of negative pole a, well-known sintered nickel positive electrode, polypropylene system and the aqueous solution that contains 30 weight %KOH that is used as alkaline electrolyte, make the cadmium-nickel storage cell A of the nominal capacity 1.4Ah of SC size.
Embodiment 2
Fig. 2 is the cross-section model of the made cadmium cathode of present embodiment.
Preparation by with embodiment 1 in made pole plate X1 constitute identical punch metal 23 and contain the pole plate X1 ' that the anode mixture layer 22 of cadmium constitutes, the surface coated of anode mixture layer 22 has the phenoxyacetic acid as aromatic carboxylic acid.Be to implement negative electrode in the nickel sulfate solution of 30g/L to decompose (Overcast decompositions) at nickel ion concentration then, the metal nickel dam 24 in the porous of the surface of pole plate X1 ' formation thickness 0.5 μ m obtains pole plate Y1.This pole plate Y1 is immersed in the potassium hydroxide aqueous solution of 30 ℃ of proportions 1.23, temperature, makes cadmium oxide be converted into cadmium hydroxide, obtain pole plate Y2.
Then, with pole plate Y2 be immersed in embodiment 1 in the used identical mixed aqueous solution, drying forms the resin bed 21 of about 0.1～2 μ m of thickness on the metal nickel dam 24 of pole plate Y2.Finished paste formula cadmium cathode b like this.
Use the dividing plate and the alkaline electrolyte of negative pole b, well-known sintered nickel positive electrode, polypropylene system, make the cadmium-nickel storage cell B of the nominal capacity 1.4Ah of SC size.
Comparative example 1
Pole plate X2 former state made among the embodiment 1 as paste formula cadmium cathode c, is used the dividing plate and the alkaline electrolyte of this negative pole c, well-known sintered nickel positive electrode, polypropylene system, make the cadmium-nickel storage cell C of the nominal capacity 1.4Ah of SC size.
Comparative example 2
Pole plate Y2 former state made among the embodiment 2 as paste formula cadmium cathode d, is used the dividing plate and the alkaline electrolyte of this negative pole d, well-known sintered nickel positive electrode, polypropylene system, make the cadmium-nickel storage cell D of the nominal capacity 1.4Ah of SC size.
Comparative example 3
1700), 2 weight account polyethylene alcohol (number average degree of polymerization: 1700) and in the aqueous solution that constitutes of 100 weight parts waters pole plate X1 made among the embodiment 1 is immersed in by 8 weight account polyethylene pyrrolidones (number average degree of polymerization:, dry, form the resin bed of about 3～8 μ m of thickness on pole plate X1 surface, obtain sticking with paste formula cadmium cathode e
Use the dividing plate and the alkaline electrolyte of this negative pole e, well-known sintered nickel positive electrode, polypropylene system, make the cadmium-nickel storage cell E of the nominal capacity 1.4Ah of SC size.
In addition, the alkaline electrolyte among battery B～E all uses the aqueous solution of KOH30 weight %.
[cell evaluation]
(i) cycling life test
With battery A～E respectively each 10, under 20 ℃ temperature atmosphere, placing 8 hours after 1.5 hours with the current charges of 1.4A under 20 ℃ the temperature atmosphere, repeat to make the circulation of end voltage discharge with the electric current of 1.4A up to 1.0V.And, obtain discharge capacity of the cell and reach 60% o'clock charge and discharge cycles number of times with respect to the discharge capacity of circulation for the first time, with this as battery life.
The charge and discharge cycles number of this moment and the relation of battery capacity are shown among Fig. 3.In addition, in the charge and discharge cycles process, battery is disintegrated by per 100 circulations, will the chemical analysis results of cadmium amount in the dividing plate be shown among Fig. 4.Discharging and recharging the back in addition and placed 8 hours, is can obviously detect for the pettiness short circuit that makes inside battery.
As shown in Figure 3, the good order of battery life is 400 circulations of battery C, D600 circulation of battery, 800 circulations of battery E, 850 circulations of battery A, 870 circulations of battery B.When judging that these batteries arrive the life-span, investigated the reason that battery disintegrates, no matter find its reason all is the internal short-circuits that caused by migration in which battery.In addition, as shown in Figure 4, along with the carrying out of charge and discharge cycles, stripping is put aside in dividing plate to the cadmium in the electrolyte.
As known from the above owing to only contain above-mentioned reinforcing agent in its negative pole of battery C as adhesive, so cadmium easily from the negative pole stripping, its life-span is the shortest.In addition, battery A, battery B, battery D, battery E because negative terminal surface has formed some films, have improved so compare the life-span with battery C, and wherein the raising of the life-span of battery B, battery A is many especially.
(ii) charge-discharge characteristic
With each battery of battery A～E under 20 ℃ the temperature atmosphere with the current charges of 1.4A after 1.5 hours, after placing 1 hour under 20 ℃ the temperature atmosphere, make the end voltage discharge up to 0.8V with the big electric current of 10A.Discharge curve therebetween is shown among Fig. 5.
As shown in Figure 5, for cell voltage, battery B and battery D height, next battery A and battery C height, the voltage of battery E is compared cell voltage with other batteries and is significantly reduced.Can think this be because, the resin bed thickness that the anode mixture layer of battery E is surface-coated, for non-conductive, so compare with battery A～D, the conductivity of battery E negative terminal surface is low.Can infer because the metal nickel dam that battery B and battery D nearby have porous in negative terminal surface, so its negative pole conductance than the height of battery A and battery C, so cell voltage is also high.
In sum, according to the present invention, there is resin bed on the cadmium cathode surface, the aforementioned resin layer is made of with product and polyvinylpyrrolidone the polyvinyl alcohol addition reaction stibazole salt, so can suppress to follow of the stripping of the cadmium of charge and discharge cycles, the cadmium-nickel storage cell that has extended cycle life can be provided to alkaline electrolyte.

Claims (5)

1. cadmium cathode, it is the cadmium-nickel storage cell cadmium cathode, resin bed by pole plate and the described polar board surface of lining is formed, and described pole plate is active material with the cadmium compound, and described resin bed is made up of the product and the PVP of the addition reaction of stibazole salt and polyvinyl alcohol.
2. according to the cadmium cathode of claim 1, wherein, between described pole plate and described resin bed, has the conductive layer of forming by metallic nickel.
3. prepare cadmium-nickel storage cell with the method for cadmium cathode, be coated in aforementioned polar board surface or aforementioned pole plate is immersed in operation c in the aqueous solution as the operation b of the aqueous solution of the product of the operation a of the pole plate of active material, addition reaction that preparation contains stibazole salt and polyvinyl alcohol and polyvinylpyrrolidone and with aqueous solution with cadmium compound comprising obtaining.
4. according to the method for preparing cadmium cathode of claim 3, wherein before operation c, also have at described polar board surface by electroplating the operation that forms the conductive layer that constitutes by metallic nickel.
5. cadmium-nickel storage cell, it is made up of nickeliferous positive pole, the described cadmium cathode of claim 1, dividing plate and alkaline electrolyte between described positive pole and negative pole.
CNB021505802A 2001-11-21 2002-11-21 Cadmium cathode and Ni-Cd accumulator comprising same Expired - Fee Related CN1199299C (en)

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JP2001355832A JP3644427B2 (en) 2001-11-21 2001-11-21 Cadmium negative electrode and nickel cadmium storage battery containing the same
JP355832/2001 2001-11-21

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CN1199299C true CN1199299C (en) 2005-04-27

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WO2006001022A1 (en) * 2004-06-28 2006-01-05 Power Paper Ltd Novel electrodes and uses thereof
CN101593833B (en) * 2008-05-28 2011-12-14 比亚迪股份有限公司 Nickel-cadmium cell cathode, manufacturing method thereof and cell with same
CN101609889B (en) * 2008-06-20 2011-11-16 比亚迪股份有限公司 Cadmium negative pole, preparation method thereof and secondary nickel-cadmium battery containing same
US20110136005A1 (en) * 2009-12-04 2011-06-09 Gregory Scott Callen Vitamin B12 iron battery
CN103151500B (en) * 2013-02-06 2015-04-22 广州市云通磁电有限公司 Manufacturing method of nickel-cadmium battery cadmium negative electrode

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US4990414A (en) * 1989-02-09 1991-02-05 Sanyo Electric Co., Ltd. Cadmium negative electrode for use in an alkaline storage cell and its manufacturing method
JP2994850B2 (en) 1992-03-31 1999-12-27 三洋電機株式会社 Paste cadmium negative electrode for alkaline storage batteries
JP2001357842A (en) * 2000-06-16 2001-12-26 Matsushita Electric Ind Co Ltd Nickel-cadmium storage battery, cadmium negative electrode, and its manufacturing method

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US20030104271A1 (en) 2003-06-05

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